Production of valuable products by conversion of carbonaceous materials



.March 12, 1935- R. WIETZEL ET AL 1,994,058 PRODUCTION OF VALUABLE PRODUCTS BY CONVERSION 01 CARBONACEOUS MATERIALS FiledAug. 26, 1929 Ruoou W/ETZEL BRUNO ENGEL,

By MMW T TORNEVSA Patented Mar. 12, 193

PRODUCTION OF VALUABLE PRODUCTS BY CONVERSION OF CARBONACEOUS MATE- RIALS Rudolf Wietzel and Bruno Engel, Ludwigshafenon-the-Rhine, Germany, assignors to I. G. Farbenindustrie Aktiengesellschaft, Frankfort-onthe-Main Germany, a corporation of Germany Application August 26, 1929, Serial No. 388,612

In Germany June 1, 1927 8 Claims. (Cl. 196-52) The subject matter of this application is a continuation-in-part of the subject matter of our copending application Ser. No. 280,114; filed May 23rd 1928, now Patent No. 1,925,551, for an 5 invention relating to the production of valuable products, such' as hydrocarbons and oils from carbonaceous materials. I

The present invention relates to the recovery may be varied within wide limits according to the character of the substances under treatment.

Materials suitable for treatment comprise, for example, the residues from the distillation of tar, cracking residues, crude mineral oils, the 5 residues from the extraction of coal and the like,

of valuable hydrocarbons and oils from mixtures thereof with solid substances, and to the production of the said hydrocarbons and oils from ca bonaceous materials.

We have found that such hydrocarbons and oils may be recovered with particular advantage particular from the crude solid or pasty products obtained by low temperature carbonization, cracking and extraction of carbonaceous materials, andin the destructive hydrogenation of coals, tars, mineral oils and the like, and which consists of mixtures of oils and other valuable hydrocarbons with soil substances such as carbonaceous residues ash constituents, or other solid admixtures such as catalysts, by stirring the mixture, preferably at a slightly elevated temperature, with a liquid in which the oil is insoluble, or only slightly soluble, and to which an alkaline reaction'has been imparted and which contains small amounts of a wetting or' emulsifying agent, such as sulphonic-acids of aromatic or aliphatic hydrocarbons, in particular nucleoalkylated sulphonic acids of aromatic hydrocarbons, cellulose pitch, saturated or unsaturated fatty acids, their salts and derivatives, glue, saponines, dextrine, oxidation products of paraflins, and the like. Products obtained by sulphonating products of the destructive hydrogenation of coal, tars and the like are also suitable.

When the adhesion between the solid substances and theoils has been sufliciently loosened,

, the oil is separated in various ways, as for example mechanicallyras by centrifugal means, preferably in the warm, or by means of electric or magnetic fields or in. other suitable ways, or

. by the application of several methods of separation simultaneously.

The process may be applied alone or in combination with other methods, such as subsequent low temperature carbonization, or extraction and the like; and the mixtures may also be subjected to repeated treatment and to the action of different kinds of liquids. The conditions inrespect of pressure and temperature from mixtures thereof with solid substances, in

or the residues obtained in the heat treatment under pressure, with or without hydrogen, of coals, peat, cellulose, tar, oils, bitumen or other carbonaceous substances. 10

Ithas also been found "suitable,- in treating the oleaginous sludge, to employ solutions which alsoecontain salts such as chlorides, sulphates and the like. If the concentration of these be such that the specific gravity of the solutions is 5 equal to, or greater than that of the solids to be separated, it is easy to carry on the operations, for instance the centrifuging, continuously.

In certrifuging especially, there is no need to stir up the sludge under treatment with the 20 added liquid beforehand in a special stage of' the process, but the material under treatment and the added liquid may vbe introduced simultaneously into the separator, such as a centrifuge. This not only saves one working stage, 25

' but also, in certain circumstances, leads to a better separation of the oil and solid residue. The rate of separation of the material on the one hand, and the added liquid on the other, depends on the character of the former.

The amount of emulsifying and wetting agents to beadded is usually very small, for .example 0.05 per cent or sometimes still less. The optimum quantity depends on the characterof the material under treatment in each case. The 35 other working conditions, such as temperature, speed of the centrifuge and the like, also depend on the material under treatment and on the wetting agent used, and must be determined by experiment in each case. For example, in centrifuging a coal sludge, such as is obtained, for example, in the extraction of coal with solventsunder pressure, it is preferable to work at a temperature not exceeding to C. when an equal quantity of an 0.05-0.1 per cent aqueous solution, for example of alkylated naph-. thalene sulphonic acids, is added to the sludge during the centrifuging process. I

The added liquid after being freed from oil 50 by centrifuging may be used over again. J

The employment of the said substances adapted to reduce the surface tension, especially the emulsifying and wetting agents, for example,

the organic substances, which contain the rad- 55- "passing into solution is hydrogenated, especially these processes combined, since excellent yieldsof valuable, and especially liquid hydrocarbons are obtained.

These processes are hereinafter referred to for the sake of brevity as the production of, valuable products by heat treatment of carbonaceous materials. The liquid employed in this case need not necessarily be rendered alkaline, although in some cases, this may be advantageous.

This process is especially adapted for the extraction of any kind of coal, under pressure, with liquid organic solvents, comprising a great variety of substances (especially those of high boiling point range), and particularly fractions or transformation products of mineral oils or tars, such as cresols, xylene, naphthalene, anthracene oil, hydrogenation products of naphthalene or benezene, or mixtures of benzene and gllsohol' or halogenated hydrocarbons and the The process may also be employed with advantage in the destructive hydrogenation, and also in cracking, since the said additions exert laik splitting action on the hydrocarbons and the The operation may be conducted under high pressures, such as 200 atmospheres, and when required, with special addition of hydrogen or other gases, and also at pressures as low as about 50 atmospheres, in which event the excess pressure generated under certain conditions by the liberation of gases from the coal," is released.

If the operation be carried on in the presence of hvdrogen, a portion of the coaly substance at temperatures above 400 C.

In addition to the substances added to reduce the surface tension of the resulting liquid products, other inorganic or organic substances, such as alkalies, zinc oxide, magnesia and the like,

- thereof unnecessary.

The following examples will further illustrate .the nature of the said invention which, however, is not restricted thereto. The parts where not otherwise stated, are by weight.

Example 1 Brown-coal is stirred up with t'etrahydronaphthalene, with an atidition of 0.05 per cent of sodium isopropylnaphthalene sulphonate, and

' heated to 350 C. under pressure. The coal is transformed into products soluble in benzene,

which amount to about '15 to 80 per cent of Example 2 100 parts of crude mineral oil, containing 4 per cent of constituents boiling up to 180 C.,' are heated with 5 parts of benzenesulphonic acid. 22.5 parts of a mixture of crude hydrocarbons boiling up to 180 C., are distilled over.

Example 3 100 parts of a brown-coal producer tar, containing no constituents boiling below 220 C., are heated in the presence of 5 parts of phenol borate, 35 parts of a mixture of hydrocarbons,

boiling up to 220 0 being distilled over.

' Example 4 Brown coal (lignite) is treated similarly as described in Example 1 but at a temperature of between 460 to 470 C. and in the presence of hydrogen at a pressure of 200 atmospheres. About 60 percent or more of the brown coal are then converted in part into liquid and also in part into solid hydrocarbons, such as paraflln wax which after separation from the undecomposed coal may be converted in known manner into benzine. If an emulsifying agent be not employed,.only about 40 to 50 percent of the initial material are converted into the aforesaid hydrocarbons.

We claim:

1. In a process for splitting high boiling hydrocarbons into lower boiling hydrocarbons without the addition thereto of substantial quantities of water, ,the step of adding'to the hydrocarbons to be split an organic emulsifying and wetting agent capable of reducing the surface tension of the products resulting-from the splitting and selected from the group consisting of aromatic and aliphatic sulphonic acids and their alkali metal salts, cellulose pitch, saturated and unsaturated fatty acids, their salts and derivatives, glue, saponins, dextrine and oxi-' dation products of parafllns.

2. The process according to the preceding 7 claim in which the wetting agent employed is an alkylated aromatic sulphonic acid.

3. The process according to claim 1 in which the wetting agent employed is sodium iso-propyl naphthalene sulphonater 4. The process according to claim 1 in which the wetting agent employed is benzene sulphonic acid.

5. In the cracking of high boiling hydrocarbons to lower boiling hydrocarbons without the addition thereto of substantial quantities of water, the step of adding to the initial material to be cracked an organic emulsifying and wetting agent capable of reducing the surface tension of the products resulting from the cracking and \selected from the group consisting of aromatic and aliphatic sulphonic acids and their alkali 7 metal salts, cellulose pitch, saturated and unsaturated fatty acids, their salts and derivatives, glue, saponins, dextrinra'nd oxidation products of paramns.

6. In' the destructive hydrogenation of high 'boiling hydrocarbons to lower boiling hydrocarbons without the addition of substantial quantities of water, the step of adding to the-initial material to be destructively hydrogenated an orand selected from the group consisting of arcclaim in which the wetting agent employed is matic and aliphatic sulphonic acids and their analkylated aromatic sulphonic acid. alkali metal salts, cellulose pitch, saturated 8. The process according to claim 6 in which and unsaturated fatty acids, their salts and dethe wetting agent employed is sodium iso-propyi 5 riyatives, glue, saponins, dextrine andoxidation naphthalene sulphonate. products or RUDOH" WIEI'LEL. 'L-The process accordins to the preceding BRUNOENGEL. 

